CN107189048A - Low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof - Google Patents
Low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof Download PDFInfo
- Publication number
- CN107189048A CN107189048A CN201710419923.4A CN201710419923A CN107189048A CN 107189048 A CN107189048 A CN 107189048A CN 201710419923 A CN201710419923 A CN 201710419923A CN 107189048 A CN107189048 A CN 107189048A
- Authority
- CN
- China
- Prior art keywords
- copolyesters
- construction unit
- iii
- unit number
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Abstract
The invention discloses low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof, the copolyesters is made up of I, II, III construction unit represented, when the construction unit number of [III] is the 3~20% of the construction unit number of [I], its intrinsic viscosity is 0.63~1.21dL/g;Limited oxygen index is 26.0~35.0;0 grade of 2~V of vertical combustion grade V;Peak value HRR PHRR is than pure PET reductions by 22.2~69.4% in taper calorimetric test, and total cigarette release TSR is than pure PET reductions by 17.7~30.6%.Due to present invention introduces fragrant nitrile structure the trimerization reaction formation conjugation triazine ring more stable than aromatic ring can occur in burning, greatly improve material melt viscosity can also aromatization chemical conversion charcoal, form a large amount of fine and close layer of charcoal, thus copolyesters has low cigarette release, excellent fire resistance and anti-dropping.Cost of material needed for the copolyesters is low, and preparation process power consumption is low, more industrialized production advantage.
Description
Technical field
The invention belongs to low-smoke and flame retardant anti-dropping copolyesters and its preparing technical field.Specifically, the present invention relates to
Copolyesters of new low-smoke and flame retardant anti-dropping of trimerization reaction formation conjugation triazine ring and preparation method thereof can occur under high temperature.Should
Class copolyesters need not add extra flame-retardant monomer, only need to introduce the modification containing fragrant nitrile structure of lower content (≤15%)
Monomer, so that it may occur the trimerization reaction formation conjugation triazine ring more more stable than aromatic ring using fragrant nitrile structure is quick in burning, no
Be only capable of greatly improving material melt viscosity can also further aromatization chemical conversion charcoal, a large amount of fine and close layer of charcoal formed can completely cut off flue gas
Release, therefore the cigarette release of polyester can be reduced, assign polyester excellent fire resistance and anti-dropping.
Background technology
Polyethylene terephthalate (polyester, PET) has very as one of maximum synthesis high polymer material of yield
Good mechanical strength, chemical resistance, heat endurance, the transparency and machinability, is widely used in engineering plastics, packaging
Many fields such as material and synthetic fibers, it is seen everywhere in daily life and working environment.But PET is highly combustible, pole
Limited oxygen index (LOI) is only 21-22, and serious molten drop phenomenon can be also produced in combustion and substantial amounts of heat and cigarette is discharged,
Not only easily accelerate flame transmission, be also easy to cause the death by suffocation of personnel.Widely using for polyester product, undoubtedly brings
Larger potential fire threat, once occur fire, it would be possible to cause serious casualties and huge property loss.Cause
This academia and industrial quarters are researching and developing the polyester with the release of low cigarette, high flame retardant and anti-dropping always.
For polyester it is inflammable the problem of, blending or copolymerization by way of, phosphorus flame retardant is incorporated into polyester, is mesh
Preceding polyester flame-retardant most effective way, i.e., only introduce a small amount of P elements with regard to that can assign polyester good fire resistance (limit oxygen
Index >=28.0, low-heat release).But the fire retardant mechanism of most of phosphorous-containing polyester is to promote molten drop to take away heat, therefore in combustion
Still can occur serious molten drop during burning as polyester, molten drop can not only trigger " second-time burning ", it is also quite conceivable to artificial
Into scald (Wang Yuzhong writes, the flame-retarded design of polyester fiber, Sichuan Science Press, 1994).Moreover, due to P elements
In the presence of phosphorous copolyester can discharge more cigarettes and carbon monoxide when burning, and visibility is reduced in a fire, increase personnel escape
Difficulty, or even personnel's Poisoning choke can be caused dead.
The problem of in order to solve polyester " fire-retardant and anti-dropping contradiction ", patent of invention ZL201410629255.4 is by ethoxy
Phenyl phosphinic acid, phosphorous-containing polyester dihydric alcohol, isocyanuric acid ester is introduced into polyester three (2- ethoxys), although it can reach preferably
Fire resistance and anti-dropping, it is distinctly understood that it is that introducing nitrogen and P elements can be only achieved simultaneously, thus will certainly
The heat endurance of polyester is destroyed, the application of material is limited;Patent of invention ZL201210382311.X is utilized and can sent out in high temperature
The azobenzene structure of biochemical crosslinking, improves melt viscosity when polyester burns and promotes material formation foamed char, but to reach
It is larger (>=20%) to monomer introduction volume when good fire resistance and anti-dropping, its fire resistance how reached in research
During with anti-dropping, the problem of cigarette discharges when not considering to solve burning.
And for ensure polyester flame-retardant anti-dropping performance while, reduction polyester burning when cigarette release report compared with
Lack, and its main method is achieved the goal while phosphonium flame retardant, fire retarding synergist is introduced by adding smoke suppressant
(such as China's application 201210581513.7).Although the addition of additive can improve fire resistance and suppress the release of cigarette, its
Compatibility of the additive not only typically with matrix is all poor, to influence the mechanical property of matrix, and with using, and it can also be from
Separate out and be discharged into environment in material, the polyester flame-retardant smoke suppressing effect for preparing such method is not lasting and can bring potential ring
The problem of border is polluted.
Content of the invention patent of invention ZL
The purpose of the present invention is that there is provided a kind of new resistance of the low cigarette based on fragrant nitrile structure the problem of presence for prior art
Fire anti-dropping copolyesters.
The second object of the present invention is to provide the preparation side of the above-mentioned low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure
Method.
The low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure that the present invention is provided, the copolyesters is by I, II, III table
The construction unit composition shown:
In formula, R1Represent arlydene,
In formula, R2Represent C2-C8Alkylidene,
In formula, R3Represent C2-C8Alkylidene, Y be O, S, Z1For H, cyano group, hydroxyl, amino, methyl, methoxyl group, tertiary fourth
Base, phenyl or phenoxy group, Z2For H, methyl, hydroxyl, amino or methoxyl group,
The construction unit number of [III] is the 3~20% of the construction unit number of [I].When [III] is B, E or H, [I]+
The construction unit number of [III]:Construction unit number=1 of [II];When [III] is A, C, D, F, G or I, the construction unit of [I]
Number:[II]+[III] construction unit number=1, R2And R3It is able to can also be differed with identical.The intrinsic viscosity of the new polyester
[η] is 0.63~1.21dL/g;Limited oxygen index is 26.0~35.0;Vertical combustion grade V-2~V-0 grades;Taper calorimetric is surveyed
Peak value HRR PHRR is than pure PET reductions by 22.2~69.4% in examination, total cigarette release TSR than pure PET reductions by 17.7~
30.6%.
In above-mentioned copolyesters, the construction unit number of [III] is the 7~15% of the construction unit number of [I].When [III] is B, E
Or during H, [I]+[III] construction unit number:Construction unit number=1 of [II];When [III] is A, C, D, F, G or I, [I's]
Construction unit number:[II]+[III] construction unit number=1, R2And R3It is able to can also be differed with identical.The spy of the new polyester
Property viscosity number [η] be 0.65~1.21dL/g;Limited oxygen index is 29.0~35.0;Vertical combustion grade V-1~V-0 grades;Taper
Peak value HRR PHRR is than pure PET reductions by 35.0~69.4% in calorimetric test, and total cigarette release TSR is reduced than pure PET
23.6~30.6%.
The preparation method of the above-mentioned low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure provided in the present invention, this method
It is under conditions of conventional catalyst, using direct esterification by the binary acid and C of equimolar amounts2~C8Dihydric alcohol carry out ester
Change after reaction or use ester-interchange method by the dibasic acid ester compound and C of equimolar amounts2~C8Dihydric alcohol carry out ester exchange reaction
Afterwards, then by polycondensation reaction it is prepared from, it is characterised in that before esterification, before esterification finishing reaction, ester exchange
Before reaction or before ester exchange reaction finishing reaction, added in reaction system with moles the hundred of binary acid or dibasic acid ester compound
Fraction is calculated as the modified monomer of 3~20% structure containing fragrant nitrile, preferably 7~15%.
The modified monomer of the structure containing fragrant nitrile used in above method is any of following general structure:
X in formula1For C2~C8Primary alcohol group, X2For hydroxyl or C1~C8Alkoxy, X3For C1~C8Alkyl, Y be O,
S, Z1For H, cyano group, hydroxyl, amino, methyl, methoxyl group, the tert-butyl group, phenyl or phenoxy group, Z2For H, methyl, hydroxyl, amino or
Methoxyl group.
Preferably any of the following general structure monomer of the monomer containing fragrant nitrile structure used in above method:
X in formula1For C2~C8Primary alcohol group, X2For hydroxyl, methoxy or ethoxy, Y is O or S, Z1For H, cyano group,
Hydroxyl, amino, methyl or methoxy, Z2For H, methyl or methoxy.
When the monomer of the structure containing fragrant nitrile added in reaction system be above-mentioned preferred monomer and content be preferred 7~
When 15%, the intrinsic viscosity of gained copolyesters is 0.65~1.21dL/g;Limited oxygen index is 30.0~35.0;Vertical combustion
Burning grade V-1~V-0 grades;Peak value HRR PHRR is than pure PET reductions by 36.3~69.4%, total cigarette in taper calorimetric test
TSR is discharged than pure PET reductions by 24.4~30.6%.
The processing step and actual conditions of direct esterification or ester-interchange method of the present invention are as follows:
Direct esterification:The modification of binary acid, dihydric alcohol, catalyst and the structure containing fragrant nitrile is added by proportioning in a kettle.
Monomer, pressurization is warming up to 200~220 DEG C and carries out 2.0~4.0h of esterification;It is low at 230~240 DEG C after esterification terminates
0.5~1.0h of polycondensation reaction under conditions of vacuum, then at 250 DEG C, 1.0~2.5h of polycondensation under conditions of high vacuum;Complete contracting
After poly- reaction, nitrogen is filled with a kettle., melt is extruded, and water cooling obtains target copolyesters.Wherein, the list of the structure containing fragrant nitrile
Body may be selected before esterification or esterification finishing reaction before add reactor.
Ester-interchange method:Carboxylate, dihydric alcohol, catalyst and the structure containing fragrant nitrile of binary acid are added by proportioning in a kettle.
Modified monomer, normal pressure carries out ester exchange reaction 2.0~4.0h in 200~220 DEG C;After ester exchange reaction terminates, 230~
240 DEG C, 0.5~1.0h of polycondensation under conditions of low vacuum, then at 250 DEG C, 1.0~2.5h of polycondensation under conditions of high vacuum;It is complete
Into after polycondensation reaction, nitrogen is filled with a kettle., melt is extruded, and water cooling obtains target copolyesters.Wherein, structure containing fragrant nitrile
Monomer may be selected before ester exchange reaction or ester exchange reaction finishing reaction before add reactor.
In above method selected catalyst be zinc acetate, manganese acetate, cobalt acetate, antimony oxide, antimony glycol and
At least one of titanate esters.
The present invention has advantages below:
1. fragrant nitrile structure is provided in the construction unit of low-smoke and flame retardant anti-dropping copolyesters provided due to the present invention, and the knot
The trimerization reaction formation conjugation triazine ring (referring to Fig. 1) more more stable than aromatic ring can quickly occur in burning for structure, can not only be big
The big melt viscosity for improving material (referring to Fig. 2), moreover it is possible to further aromatization chemical conversion charcoal, forms a large amount of fine and close layer of charcoal (referring to figure
3), oxygen barrier is heat-insulated, assigns polyester good self-extinguishment, even if so that the copolyesters hinders without traditional halogen system and phosphorus system
Agent is fired, only excellent fire resistance can be just obtained simultaneously (referring to figure in the case where introducing less fragrant nitrile structure (≤15%)
4) with anti-dropping.
2. fragrant nitrile structure is provided in the copolyesters provided due to the present invention, and fragrant nitrile structure can be formed quickly in burning
Stable conjugation triazine ring, and further aromatization chemical conversion charcoal, form a large amount of fine and close layer of charcoal, can not only reduce the life of gas-phase product
Into, moreover it is possible to obstruct flue gas loss, thus make the copolyesters that there is low cigarette to discharge (referring to Fig. 5), it is to avoid prior art passes through
The problem of additives such as addition smoke suppressant are brought.
3. containing fragrant nitrile structure in the copolyesters provided due to the present invention, it can quickly be formed in burning using it and compare aromatic ring
More stable triazine ring and aromatization chemical conversion charcoal, the characteristic of a large amount of fine and close layer of charcoal of formation, with regard to copolyesters can be made to obtain low cigarette release, height
Fire resistance and anti-dropping, therefore avoid because adding traditional phosphorus flame retardant potentially producing in combustion for bringing
It is the problem of raw serious molten drop and release a large amount of pernicious gases, more friendly to environment.
4. fragrant nitrile structure has been only introduced in the copolyesters provided due to the present invention, and fragrant nitrile structure is not strong chromophore,
Therefore copolyesters of light color can be prepared, and the copolyesters need not add fire retardant, thus it possesses excellent add
Work.
5. the modified monomer needed for the copolyesters provided due to the present invention is the compound containing fragrant nitrile structure, and such
The cost of compound is low, and synthesis step is simple, and yield is high, and the polymerization temperature needed for copolyesters it is low (230~250 DEG C, polyester
260~270 DEG C of polymerization temperature), energy consumption can be substantially reduced, thus the copolyesters has more the advantage of industrialized production.
6. the copolyesters that the present invention is provided can be used directly as fibrous raw material, engineering plastics and film materials.
Brief description of the drawings
The schematic diagram of trimerization reaction occurs in burning for fragrant nitrile structure in the copolyesters that Fig. 1 provides for the present invention.Fragrant nitrile knot
In burning intermolecular trimerization reaction can occur for structure, form the conjugation triazine ring structure more stable than aromatic ring, this knot
Structure can not only greatly improve material melt viscosity can also aromatization chemical conversion charcoal, form a large amount of fine and close layer of charcoal, this pair drops simultaneously
The release of oligoester cigarette, raising fire resistance and anti-dropping can serve vital.
Fig. 2 is copolyesters prepared by the embodiment of the present invention 6 and the pure PET of comparative example alternating temperature rheometer test curve map (material
The higher melt viscosity for meaning material in burning of complex viscosity in high temperature is higher, and the ability of anti-dropping is stronger).With it is pure
The trend that PET complex viscosity raises gradually step-down with temperature is different, and the complex viscosity of copolyesters of the present invention is with temperature
Rise can raise rapidly, i.e., from 230 DEG C to 300 DEG C, the complex viscosity of copolyesters increases about 40 times.
Fig. 3 is the digital photograph of the copolyesters and pure PET of the preparation of the embodiment of the present invention 6 after limited oxygen index test.From
The visible pure PET of photo is generated without layer of charcoal after combustion, and copolyesters prepared by the present invention can form a large amount of causes after combustion
Close layer of charcoal, fine and close layer of charcoal can oxygen barrier be heat-insulated and barrier flue gas release.
The heat release rate curve of copolyesters and the pure PET of comparative example prepared by Fig. 4 embodiments 6 in taper calorimetric test
Figure.The peak value HRR PHRR of copolyesters prepared by the present invention is than pure PET reductions by 69.4%.
Fig. 5 is the total cigarette release profiles of the copolyesters and the pure PET of comparative example of the preparation of embodiment 6 in taper calorimetric test
Figure.Total cigarette release TSR of copolyesters prepared by the present invention is more obvious than pure PET reductions.
Embodiment
Embodiment is given below so that the invention will be further described.It is necessarily pointed out that following examples can not
Be interpreted as limiting the scope of the invention, if the person skilled in the art in the field according to the invention described above content to this hair
It is bright to make some nonessential modifications and adaptations, still fall within the scope of the present invention.
In addition, what deserves to be explained is:The low-smoke and flame retardant anti-dropping copolyesters of the structure containing fragrant nitrile obtained by following examples and
The intrinsic viscosity of comparative example polyester PET is with phenol/1,1,2,2- tetrachloroethanes (1:1,v:V) it is solvent, is configured to concentration
For 0.5g/dL solution, test what is obtained at 25 DEG C with dark type viscometer;Limited oxygen index LOI is to use HAAKE Mini Jet
Pro miniature injection machines are made into 130 × 6.5 × 3.2mm3Standard oxygen exponential spline, according to ASTM D2863-13 standards,
Determine what is obtained on HC-2 oxygen index instruments;Vertical combustion grade then be with HAAKE Mini Jet Pro miniature injection machines by its
130 × 13 × 3.2mm is made3Standard batten, according to UL-94 standards, determine what is obtained using CZF-2 Vertical combustion instruments;Cone
Shape calorimetric test be it is a kind of can quantitatively analyzing material burning behavior test, using the teaching of the invention it is possible to provide many materials burn when performance number
According to peak value HRR PHRR is most important parameter in taper calorimetric test, is that judge polymeric material fire resistance is excellent
Bad primary parameter, total cigarette release TSR is to weigh the parameter that material gives birth to cigarette in combustion, and PHRR and TSR are according to ISO
5660-1 standards, in FTT cone calorimetries with 50kW/m2Measurement power be measured what is obtained, taper calorimetric test sample
Plate is 100 × 100 × 3mm being made of XK-12-024-0036 vulcanizing presses3Standard jig.
Embodiment 1
By 920g terephthalic acid (TPA)s, 353g ethylene glycol, (2- hydroxyl-oxethyls) benzonitriles of 37g 3,5- bis- and 0.360g second
Glycol antimony is added in reactor, in inflated with nitrogen exclusion kettle after air, is pressurized to 0.1MPa, 200 DEG C are warming up in 2h and is opened
Beginning esterification, it is 0.3~0.4MPa to control pressure in kettle, is maintained after 1.5h, and pressure starts temperature after reduction, 1.5h and gradually risen
To 220 DEG C, pressure is down to normal pressure, and esterification terminates;Afterwards in 230~240 DEG C of low vacuum polycondensation reaction 0.5h, then heat up
To 250 DEG C of high vacuum (pressure<60Pa) after polycondensation reaction 2h, discharging, water cooling.
The intrinsic viscosity of the copolyesters is 0.63dL/g;Limited oxygen index is 26.0;V-2 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing twice in burning drips number totally 6 drop;Peak value HRR PHRR is 482kW/m in taper calorimetric test2,
Total cigarette release TSR is 1499m2/m2。
Embodiment 2
By 920g terephthalic acid (TPA)s, 316g ethylene glycol, (2- hydroxyl-oxethyls) phthalic nitriles of 205g 3,6- bis- and 0.360g
Antimony glycol is added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, discharging.
The intrinsic viscosity of the copolyesters is 1.05dL/g;Limited oxygen index is 34.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 210kW/ in taper calorimetric test
m2, total cigarette release TSR is 1290m2/m2。
Embodiment 3
By 920g terephthalic acid (TPA)s, 298g ethylene glycol, (2- acetoxyl groups) phthalic nitriles of 268g 3,6- bis- and 0.360g second
Glycol antimony is added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, discharging.
The intrinsic viscosity of the copolyesters is 0.91dL/g;Limited oxygen index is 33.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Taper calorimetric test peak value HRR PHRR is 223kW/m2,
Total cigarette release TSR is 1295m2/m2。
Embodiment 4
By 920g terephthalic acid (TPA)s, 353g ethylene glycol, (2- hydroxyl-oxethyls) phthalic nitriles of 76g 3,6- bis- and 0.360g
Antimony oxide is added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, discharging.
The intrinsic viscosity of the copolyesters is 0.69dL/g;Limited oxygen index is 29.0;V-2 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing twice in burning drips number totally 4 drop;Peak value HRR PHRR is 460kW/m in taper calorimetric test2,
Total cigarette release TSR is 1400m2/m2。
Embodiment 5
By 920g terephthalic acid (TPA)s, 409g ethylene glycol, 171g 5- (3- cyano-benzene oxygens) DMIPs and
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 0.71dL/g;Limited oxygen index is 30.0;V-1 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 331kW/ in taper calorimetric test
m2, total cigarette release TSR is 1324m2/m2。
Embodiment 6
By 920g terephthalic acid (TPA)s, 428g ethylene glycol, 257g 5- (4- cyano-benzene oxygens) DMIP,
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 1.12dL/g;Limited oxygen index is 35.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 190kW/ in taper calorimetric test
m2, total cigarette release TSR is 1264m2/m2。
Embodiment 7
By 920g terephthalic acid (TPA)s, 391g ethylene glycol, 120g 5- (2- cyano-benzene oxygens) DMIPs and
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 0.65dL/g;Limited oxygen index is 30.0;V-1 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 395kW/ in taper calorimetric test
m2, total cigarette release TSR is 1376m2/m2。
Embodiment 8
By 920g terephthalic acid (TPA)s, 428g ethylene glycol, 270g 5- (2- cyano group -4- hydroxyphenoxies) M-phthalic acid two
Methyl esters and 0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition is esterified and polycondensation is anti-
Ying Hou, discharging.
The intrinsic viscosity of the copolyesters is 1.21dL/g;Limited oxygen index is 32.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 371kW/ in taper calorimetric test
m2, total cigarette release TSR is 1337m2/m2。
Embodiment 9
By 920g terephthalic acid (TPA)s, 391g ethylene glycol, 89g 5- (2- cyano group -4- methylphenoxies) M-phthalic acid diformazan
Ester and 0.360g antimony glycols are added in reactor, and the step of being provided by embodiment 1 and condition are esterified and polycondensation reaction
Afterwards, discharge.
The intrinsic viscosity of the copolyesters is 0.76dL/g;Limited oxygen index is 29.0;V-2 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing twice in burning drips number totally 3 drop;Peak value HRR PHRR is 412kW/m in taper calorimetric test2,
Total cigarette release TSR is 1381m2/m2。
Embodiment 10
By 920g terephthalic acid (TPA)s, 409g ethylene glycol, 180g 5- (2- cyano group -4- aminomethyl phenyls) sulfoisophthalic acid
Dimethyl ester and 0.360g antimony glycols are added in reactor, and the step of being provided by embodiment 1 and condition are esterified and polycondensation
After reaction, discharging.
The intrinsic viscosity of the copolyesters is 0.99dL/g;Limited oxygen index is 30.0;V-1 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 391kW/ in taper calorimetric test
m2, total cigarette release TSR is 1360m2/m2。
Embodiment 11
By 920g terephthalic acid (TPA)s, 524g propane diols, 277g 5- (2,3- dicyanobenzenes epoxide) DMIP
Be added to 0.360g antimony glycols in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after,
Discharging.
The intrinsic viscosity of the copolyesters is 1.10dL/g;Limited oxygen index is 35.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 193kW/ in taper calorimetric test
m2, total cigarette release TSR is 1270m2/m2。
Embodiment 12
By 920g terephthalic acid (TPA)s, 409g ethylene glycol, 185g 5- (3,5- dicyanobenzenes epoxide) DMIP
It is added to 0.360g butyl titanates in reactor, the step of being provided by embodiment 1 and condition are esterified and polycondensation reaction
Afterwards, discharge.
The intrinsic viscosity of the copolyesters is 1.19dL/g;Limited oxygen index is 34.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing drippage and produced without molten drop twice in burning;Peak value HRR PHRR is in taper calorimetric test
211kW/m2, total cigarette release TSR is 1293m2/m2。
Embodiment 13
By 920g terephthalic acid (TPA)s, 391g ethylene glycol, 92g 5- (3,4- dicyanobenzenes epoxide) DMIP
Be added to 0.360g antimony glycols in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after,
Discharging.
The intrinsic viscosity of the copolyesters is 0.84dL/g;Limited oxygen index is 27.5;V-2 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing twice in burning drips number totally 2 drop;Peak value HRR PHRR is 431kW/m in taper calorimetric test2,
Total cigarette release TSR is 1403m2/m2。
Embodiment 14
By 920g terephthalic acid (TPA)s, 428g ethylene glycol, 252g 5- (2,3- dicyano -4- hydroxyphenoxies) isophthalic diformazan
Dimethyl phthalate and 0.360g antimony glycols are added in reactor, and the step of being provided by embodiment 1 and condition are esterified and contracted
After poly- reaction, discharging.
The intrinsic viscosity of the copolyesters is 1.02dL/g;Limited oxygen index is 33.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 200kW/ in taper calorimetric test
m2, total cigarette release TSR is 1282m2/m2。
Embodiment 15
By 920g terephthalic acid (TPA)s, 594g butanediols, 189g 5- (3- cyano group -4- hydroxy phenyls) sulfoisophthalic acid
Dimethyl ester and 0.360g antimony glycols are added in reactor, and the step of being provided by embodiment 1 and condition are esterified and polycondensation
After reaction, discharging.
The intrinsic viscosity of the copolyesters is 0.91dL/g;Limited oxygen index is 33.0;V-1 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 281kW/ in taper calorimetric test
m2, total cigarette release TSR is 1301m2/m2。
Embodiment 16
By 920g terephthalic acid (TPA)s, 316g ethylene glycol, the adjacent benzene two of 281g 4- (3,5- bis- (2- hydroxy ethoxies) benzene ethyoxyl)
Nitrile and 0.360g antimony glycols are added in reactor, and the step of being provided by embodiment 1 and condition are esterified and polycondensation reaction
Afterwards, discharge.
The intrinsic viscosity of the copolyesters is 0.88dL/g;Limited oxygen index is 34.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 220kW/ in taper calorimetric test
m2, total cigarette release TSR is 1291m2/m2。
Embodiment 17
By 920g terephthalic acid (TPA)s, 428g ethylene glycol, 257g 5- (2- cyano-benzene oxygens) DMIPs and
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 0.87dL/g;Limited oxygen index is 33.5;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 260kW/ in taper calorimetric test
m2, total cigarette release TSR is 1298m2/m2。
Embodiment 18
By 920g terephthalic acid (TPA)s, 409g ethylene glycol, 185g 5- (2,3- dicyanobenzenes epoxide) DMIP
Be added to 0.360g antimony glycols in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after,
Discharging.
The intrinsic viscosity of the copolyesters is 0.95dL/g;Limited oxygen index is 32.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 316kW/ in taper calorimetric test
m2, total cigarette release TSR is 1350m2/m2。
Embodiment 19
By 920g terephthalic acid (TPA)s, 391g ethylene glycol, 111g 4,4 '-((1,3- phenylene -2- cyano group) two epoxides) hexichol
Formic acid dimethyl ester and 0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and
After polycondensation reaction, discharging.
The intrinsic viscosity of the copolyesters is 0.84dL/g;Limited oxygen index is 29.0;V-2 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing twice in burning drips number totally 2 drop;Peak value HRR PHRR is 351kW/m in taper calorimetric test2,
Total cigarette release TSR is 1321m2/m2。
Embodiment 20
By 920g terephthalic acid (TPA)s, 524g propane diols, 332g 4,4 '-((1,3- phenylene -5- cyano group) two epoxides) hexichol
Formic acid dimethyl ester, 0.190g antimony glycols and 0.190g butyl titanates are added in reactor, the step of being provided by embodiment 1
With condition be esterified and polycondensation reaction after, discharging.
The intrinsic viscosity of the copolyesters is 0.92dL/g;Limited oxygen index is 33.5;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 255kW/ in taper calorimetric test
m2, total cigarette release TSR is 1287m2/m2。
Embodiment 21
By 920g terephthalic acid (TPA)s, 409g ethylene glycol, 222g 4,4 '-((1,3- phenylene -5- cyano group) two epoxides) hexichol
Formic acid dimethyl ester and 0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and
After polycondensation reaction, discharging.
The intrinsic viscosity of the copolyesters is 0.91dL/g;Limited oxygen index is 33.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 298kW/ in taper calorimetric test
m2, total cigarette release TSR is 1305m2/m2。
Embodiment 22
By 920g terephthalic acid (TPA)s, 391g ethylene glycol, 118g 4,4 '-((1,4- phenylene -2,3- dicyanos) two epoxides)
Dibenzoic acid dimethyl ester and 0.360g antimony glycols are added in reactor, and the step of being provided by embodiment 1 and condition carry out ester
After change and polycondensation reaction, discharging.
The intrinsic viscosity of the copolyesters is 0.89dL/g;Limited oxygen index is 28.0;V-2 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing twice in burning drips number totally 3 drop;Peak value HRR PHRR is 405kW/m in taper calorimetric test2,
Total cigarette release TSR is 1409m2/m2。
Embodiment 23
By 920g terephthalic acid (TPA)s, 316g ethylene glycol, 380g 2,6- bis- (4- (2- hydroxy ethoxies) phenoxy group benzonitriles and
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 0.78dL/g;Limited oxygen index is 35.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 192kW/ in taper calorimetric test
m2, total cigarette release TSR is 1266m2/m2。
Embodiment 24
By 920g terephthalic acid (TPA)s, 335g ethylene glycol, 224g 3,5- bis- (4- (2- hydroxy ethoxies) phenoxy group benzonitriles and
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 0.73dL/g;Limited oxygen index is 33.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 235kW/ in taper calorimetric test
m2, total cigarette release TSR is 1301m2/m2。
Embodiment 25
By 920g terephthalic acid (TPA)s, 486g butanediols, (4- (2- hydroxy ethoxies) the phenoxy group phthalic nitriles of 238g 3,5- bis-
Be added to 0.360g antimony glycols in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after,
Discharging.
The intrinsic viscosity of the copolyesters is 0.69dL/g;Limited oxygen index is 34.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 241kW/ in taper calorimetric test
m2, total cigarette release TSR is 1291m2/m2。
Embodiment 26
By 920g terephthalic acid (TPA)s, 391g ethylene glycol, 111g 4,4 '-((1,4- phenylene -2- cyano group) two epoxides) hexichol
Formic acid dimethyl ester and 0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and
After polycondensation reaction, discharging.
The intrinsic viscosity of the copolyesters is 0.72dL/g;Limited oxygen index is 27.0;V-2 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing twice in burning drips number totally 4 drop;Peak value HRR PHRR is 407kW/m in taper calorimetric test2,
Total cigarette release TSR is 1422m2/m2。
Embodiment 27
By 920g terephthalic acid (TPA)s, 335g ethylene glycol, (4- acetoxyl groups) the phenoxy group benzonitriles of 222g 3,5- bis- and
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 0.68dL/g;Limited oxygen index is 32.0;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 291kW/ in taper calorimetric test
m2, total cigarette release TSR is 1294m2/m2。
Embodiment 28
By 920g terephthalic acid (TPA)s, 353g ethylene glycol, (4- acetoxyl groups) the phenyl nitriles of 192g 2,5- bis- and 0.360g
Antimony glycol is added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, discharging.
The intrinsic viscosity of the copolyesters is 1.02dL/g;Limited oxygen index is 29.0;V-1 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 403kW/ in taper calorimetric test
m2, total cigarette release TSR is 1390m2/m2。
Embodiment 29
By 920g terephthalic acid (TPA)s, 316g ethylene glycol, 359g 2,5- bis- (4- (2- hydroxy ethoxies) phenoxy group benzonitriles and
0.360g antimony glycols are added in reactor, the step of being provided by embodiment 1 and condition be esterified and polycondensation reaction after, go out
Material.
The intrinsic viscosity of the copolyesters is 0.79dL/g;Limited oxygen index is 34.5;V-0 grades of vertical combustion grade, hangs down
Direct combustion is lighted to extinguishing and produced without molten drop twice in burning;Peak value HRR PHRR is 198kW/ in taper calorimetric test
m2, total cigarette release TSR is 1270m2/m2。
Comparative example
920g terephthalic acid (TPA)s, 410g ethylene glycol and 0.360g antimony glycols are added in reactor, inflated with nitrogen is excluded
In kettle after air, be pressurized to 0.1MPa, 240 DEG C of beginning esterifications be warming up in 2h, control in kettle pressure for 0.3~
0.4MPa, is maintained after 1.5h, and pressure starts temperature after reduction, 1.5h and is gradually increased to 260 DEG C, and pressure is down to normal pressure, esterification
Terminate;Afterwards in 260~270 DEG C of low vacuum polycondensation reaction 0.5h, then in 270 DEG C of high vacuum (pressure<60Pa) polycondensation reaction
After 2.5h, discharging, water cooling.
The intrinsic viscosity of the polyester is 0.81dL/g;Limited oxygen index is 22.0;Vertical combustion grade is stepless
(N.R.), molten drop is extremely serious in vertical combustion, it is difficult to count, and flame is burnt to fixture;Peak heat discharges in taper calorimetric test
Speed PHRR is 620kW/m2, total cigarette release TSR is 1821m2/m2。
Claims (6)
1. the low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure, the copolyesters is the construction unit group represented by I, II, III
Into:
In formula, R1Represent arlydene,
In formula, R2Represent C2-C8Alkylidene,
In formula, R3Represent C2-C8Alkylidene, Y be O, S, Z1For H, cyano group, hydroxyl, amino, methyl, methoxyl group, the tert-butyl group, benzene
Base or phenoxy group, Z2For H, methyl, hydroxyl, amino or methoxyl group,
The construction unit number of [III] is the 3~20% of the construction unit number of [I], when [III] is B, E or H, [I]+[III's]
Construction unit number:Construction unit number=1 of [II];When [III] is A, C, D, F, G or I, the construction unit number of [I]:[II]+
The construction unit number=1, R of [III]2And R3It is able to can also be differed with identical;The intrinsic viscosity of the copolyesters be 0.63~
1.21dL/g;Limited oxygen index is 26.0~35.0;Vertical combustion grade V-2~V-0 grades;Peak heat is released in taper calorimetric test
Speed PHRR is put than pure PET reductions by 22.2~69.4%, total cigarette release TSR is than pure PET reductions by 17.7~30.6%.
2. in the low-smoke and flame retardant anti-dropping copolyesters according to claim 1 based on fragrant nitrile structure, the copolyesters [III]
Construction unit number is the 7~15% of the construction unit number of [I], when [III] is B, E or H, [I]+[III] construction unit number:
Construction unit number=1 of [II];When [III] is A, C, D, F, G or I, the construction unit number of [I]:[II]+[III] structure
Unit number=1, R2And R3It is able to can also be differed with identical, the intrinsic viscosity of the new polyester is 0.65~1.21dL/g;
Limited oxygen index is 29.0~35.0;Vertical combustion grade V-1~V-0 grades;Peak value HRR in taper calorimetric test
PHRR is than pure PET reductions by 35.0~69.4%, and total cigarette release TSR is than pure PET reductions by 23.6~30.6%.
3. a kind of preparation method of the low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure described in claim 1, this method
It is under the catalytic condition of conventional catalyst, using direct esterification by the binary acid and C of equimolar amounts2~C8Dihydric alcohol enter
By the dibasic acid ester compound and C of equimolar amounts after row esterification or using ester-interchange method2~C8Dihydric alcohol carry out ester exchange it is anti-
Ying Hou, then be prepared from by polycondensation reaction, it is characterised in that before esterification, before esterification finishing reaction, ester friendship
Change before reaction or before ester exchange reaction finishing reaction, mole of binary acid or dibasic acid ester compound is added in reaction system
Percentage is calculated as the modified monomer of 3~20% structure containing fragrant nitrile.
4. the preparation method of the low-smoke and flame retardant anti-dropping copolyesters according to claim 3 based on fragrant nitrile structure, this method
Added in reaction system be calculated as by the mole percent of binary acid or binary acid compound 7~15% the construction unit containing fragrant nitrile
Monomer.
5. the preparation method of the low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure according to claim 3 or 4, the party
Monomer containing fragrant nitrile structure used in method is any of following general structure:
X in formula1For C2~C8Primary alcohol group, X2For hydroxyl or C1~C8Alkoxy, X3For C1~C8Alkyl, Y be O, S, Z1
For H, cyano group, hydroxyl, amino, methyl, methoxyl group, the tert-butyl group, phenyl or phenoxy group, Z2For H, methyl, hydroxyl, amino or methoxy
Base.
6. the preparation method of the low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure according to claim 3 or 4, the party
Monomer containing fragrant nitrile structure used in method is any of following general structure:
X in formula1For C2~C8Primary alcohol group, X2For hydroxyl, methoxy or ethoxy, Y is O or S, Z1For H, cyano group, hydroxyl,
Amino, methyl or methoxy, Z2For H, methyl or methoxy, the intrinsic viscosity of gained copolyesters is 0.65~1.21dL/g;
Limited oxygen index is 30.0~35.0;Vertical combustion grade V-1~V-0 grades;Peak value HRR in taper calorimetric test
PHRR is than pure PET reductions by 36.3~69.4%, and total cigarette release TSR is than pure PET reductions by 24.4~30.6%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710419923.4A CN107189048B (en) | 2017-06-06 | 2017-06-06 | Low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710419923.4A CN107189048B (en) | 2017-06-06 | 2017-06-06 | Low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107189048A true CN107189048A (en) | 2017-09-22 |
CN107189048B CN107189048B (en) | 2019-01-01 |
Family
ID=59877757
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710419923.4A Active CN107189048B (en) | 2017-06-06 | 2017-06-06 | Low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107189048B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108395526A (en) * | 2018-02-09 | 2018-08-14 | 四川大学 | Flame-retardant anti-dripping copolyester and preparation method thereof based on benzimidazole structure |
CN110105536A (en) * | 2019-03-19 | 2019-08-09 | 广州朗腾聚氨酯有限公司 | A kind of low-smoke low-toxicity combined polyether and its polyurethane preparation method |
CN113817150A (en) * | 2020-06-19 | 2021-12-21 | 四川大学 | Copolyester containing aromatic secondary amine structure and preparation method and application thereof |
WO2021254391A1 (en) * | 2020-06-19 | 2021-12-23 | 四川大学 | High-temperature self-crosslinking-based flame-retardant droplet-resistant copolyester, and preparation method therefor and application thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021415A (en) * | 1974-02-14 | 1977-05-03 | Chang William J H | Nitrile containing aromatic polyamide polymers |
JPH03124725A (en) * | 1989-10-09 | 1991-05-28 | Tosoh Corp | Aromatic polyester |
CN101407577A (en) * | 2008-11-17 | 2009-04-15 | 四川大学 | Low-melting point phosphor-containing flame-retardant copolyester and preparation thereof |
CN102504242A (en) * | 2011-11-29 | 2012-06-20 | 电子科技大学 | Polyaryletherketone-nitrile copolymer and preparation method thereof |
CN102863611A (en) * | 2012-10-10 | 2013-01-09 | 四川大学 | Azobenzene structure based high-temperature self-cross-linked expanded flame-retardant anti-dripping copolyester and preparation method thereof |
CN103665358A (en) * | 2013-10-16 | 2014-03-26 | 上海大学 | Phosphorus-nitrogen copolyester material containing cyclotriphosphonitrile group and preparation method thereof |
CN104710604A (en) * | 2015-03-13 | 2015-06-17 | 四川大学 | Branching, cross-linking, expanded, melt-dropping-resistant and flame-retardant copolyester based on triazine ring structure and preparation method of copolyester |
CN105061262A (en) * | 2015-08-24 | 2015-11-18 | 广东顺德高耐特新材料有限公司 | Low-melting-point aromatic-nitrile-group resin monomer and preparation thereof and aromatic-nitrile-group polymer and preparation method thereof |
-
2017
- 2017-06-06 CN CN201710419923.4A patent/CN107189048B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4021415A (en) * | 1974-02-14 | 1977-05-03 | Chang William J H | Nitrile containing aromatic polyamide polymers |
JPH03124725A (en) * | 1989-10-09 | 1991-05-28 | Tosoh Corp | Aromatic polyester |
CN101407577A (en) * | 2008-11-17 | 2009-04-15 | 四川大学 | Low-melting point phosphor-containing flame-retardant copolyester and preparation thereof |
CN102504242A (en) * | 2011-11-29 | 2012-06-20 | 电子科技大学 | Polyaryletherketone-nitrile copolymer and preparation method thereof |
CN102863611A (en) * | 2012-10-10 | 2013-01-09 | 四川大学 | Azobenzene structure based high-temperature self-cross-linked expanded flame-retardant anti-dripping copolyester and preparation method thereof |
CN103665358A (en) * | 2013-10-16 | 2014-03-26 | 上海大学 | Phosphorus-nitrogen copolyester material containing cyclotriphosphonitrile group and preparation method thereof |
CN104710604A (en) * | 2015-03-13 | 2015-06-17 | 四川大学 | Branching, cross-linking, expanded, melt-dropping-resistant and flame-retardant copolyester based on triazine ring structure and preparation method of copolyester |
CN105061262A (en) * | 2015-08-24 | 2015-11-18 | 广东顺德高耐特新材料有限公司 | Low-melting-point aromatic-nitrile-group resin monomer and preparation thereof and aromatic-nitrile-group polymer and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
DE-MING GUO,等: "A new approach to improving flame retardancy, smoke suppression and anti-dripping of PET: Via arylene-ether units rearrangement reactions at high temperature", 《POLYMER》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108395526A (en) * | 2018-02-09 | 2018-08-14 | 四川大学 | Flame-retardant anti-dripping copolyester and preparation method thereof based on benzimidazole structure |
CN108395526B (en) * | 2018-02-09 | 2020-03-10 | 四川大学 | Flame-retardant anti-dripping copolyester based on benzimidazole structure and preparation method thereof |
CN110105536A (en) * | 2019-03-19 | 2019-08-09 | 广州朗腾聚氨酯有限公司 | A kind of low-smoke low-toxicity combined polyether and its polyurethane preparation method |
CN113817150A (en) * | 2020-06-19 | 2021-12-21 | 四川大学 | Copolyester containing aromatic secondary amine structure and preparation method and application thereof |
WO2021254391A1 (en) * | 2020-06-19 | 2021-12-23 | 四川大学 | High-temperature self-crosslinking-based flame-retardant droplet-resistant copolyester, and preparation method therefor and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN107189048B (en) | 2019-01-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107189048B (en) | Low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof | |
CN108395526A (en) | Flame-retardant anti-dripping copolyester and preparation method thereof based on benzimidazole structure | |
CN102863611B (en) | Azobenzene structure based high-temperature self-cross-linked expanded flame-retardant anti-dripping copolyester and preparation method thereof | |
CN105273173B (en) | High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure and preparation method thereof | |
CN101508770B (en) | Method for preparing phosphor system halogen-free flame-proof copolymerization polyester | |
CN104710604B (en) | Branched crosslinking expansion melt-drip resistant inflaming retarding copolyesters based on triazine ring structure and preparation method thereof | |
CN102174183B (en) | High-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparation method thereof | |
CN101225158B (en) | Phosphoric flame-proof copolyester ionomer and preparation method thereof | |
CN110746457B (en) | Ionic monomer containing phosphonate structure, flame-retardant smoke-suppressing ionomer catalytically synthesized by using ionic monomer, and preparation methods and applications of ionic monomer and ionomer | |
CN104592094B (en) | Monomer containing benzimide phenylacetylene structure, high temperature self-crosslinked copolyester and preparation method thereof | |
CN104231250A (en) | Cationic dyeable flame-retardant polyester and preparation method thereof | |
CN101974148B (en) | High-molecular weight phosphorous flame retardant random copolyester and preparation method thereof | |
CN108359084B (en) | High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzimide structure and preparation method thereof | |
CN104119538A (en) | Flame retardant and preparation method thereof, and flame-retardant polyester and application thereof | |
CN110016054A (en) | The ion monomer of phosphorus-nitrogen containing benzheterocycle structure, with its fire-retardant copolymerization ester type ionomer and their preparation method and application | |
CN101130601A (en) | Flame retardance poly- p-benzene dicarboxylic acid trimethylene glycol ester and method for producing the same | |
CN113817152B (en) | Flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking and preparation method and application thereof | |
CN109517152B (en) | High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzamide structure and preparation method and application thereof | |
CN108383987A (en) | Height based on arone structure is at charcoal low-smoke and flame retardant anti-dropping copolyesters and preparation method thereof | |
CN101148498A (en) | Degradable anti-flaming copolyester, preparation method thereof and mixing material prepared from the same and aliphatic polyester | |
Zheng et al. | Natural polyphenol-inspired polymer towards multifunction and high performance | |
CN113817150B (en) | Copolyester containing aromatic secondary amine structure and preparation method and application thereof | |
CN104478789A (en) | Copolyester crosslinking monomer, copolyester based on monomer and preparation method thereof | |
CN101525420B (en) | Fire retardant polyethylene terephthalate | |
JP2023531467A (en) | Flame-retardant and anti-drip copolyester based on high temperature self-crosslinking and its preparation and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |